Compositions of hydraulic fracturing fluid and method thereof

ABSTRACT

A hydraulic fracture fluid is provided. The fluid can include a liquid solvent, one or more surfactants, a proppant-forming compound, and one or more curing agents. The liquid reacts to form proppant in-situ under downhole conditions.

FIELD

The disclosure relates generally to subterranean formation treatments.The disclosure relates specifically to proppants in a hydraulicfracturing fluid for oil and gas recovery improvement.

BACKGROUND

Hydraulic fracturing has been an important technique to enhanceproduction of hydrocarbon from oil and gas bearing formation. In atypical hydraulic fracturing treatment, hydraulic fracturing fluidcontaining a solid proppant is injected into the formation at a pressurehigh enough to cause or enlarge a fracture in the reservoir. When thehydraulic fracturing fluid is removed, packed proppant can keep thefracture open, allowing fluids to flow from the formation through theproppant to the production wellbore. The proppant is of extremeimportance as it provides a long-term conductivity of the fracture.

The main function of proppants is to provide and maintain conductivefractures where proppants should meet closure stress requirement andshow resistance to diagenesis under downhole conditions. Differentproppants have been developed to meet the requirement of enhancingproduction of hydrocarbon with various materials, sizes and shapes. Manymaterials have been used as proppants including silica sand, glass andceramic. The hydraulic fracturing fluid carrying the proppant in thefracture generally contains water, polymer, crosslinker, fluid lossadditives, surfactants, flow back additives, surfactants, claystabilizers, proppant, and gel breaker. The polymer is used to provideviscosity and keep the proppants suspended until they have reached theirdesired location in the fracture. The breakers are used to reduce thepolymer viscosity, allowing the particles to settle and the liquidportion of the fracturing fluid to be returned to the surface when theexternal pressure is removed. The proppants remain in the fracture andform permeability channels to increase the oil or gas production.

The success of the fracturing treatment may depend on the permeabilityof the proppant. U.S. Pat. No. 7,581,590 to Timothy Lesko et al.discloses a method of heterogeneous proppant placement in a fracture.The method is based on the concept that proppant can be placeddiscontinuously within the fracture. This technique uses a pumpingscheme where proppant is added in short pulses, alternating with pulseswithout proppant. Specialized fibers render the integrity of theproppant pulses by binding the proppant particles together, thus keepingthe proppant in the form of individual clusters in the fracture. In thisway, hydrocarbons can flow through the channels separating the proppantclusters rather than flowing through the proppant pack itself as inconventional fractures. From this principle, the conductivity of thechannel fracturing technique would well exceed that of a continuousproppant pack, resulting in improved hydrocarbon productions.

The conventional proppants have certain disadvantages such as formationand fracture permeability damage due to the viscous gel residue, risk ofearly screen-out and reduced effective propped area due to proppantexcessive leakoff or settling, and abrasion to the pumping equipment andtubular. To eliminate the effect of some disadvantages, and have moreapplication potential, U.S. Pat. No. 9,834,721 to Fakuen Frank Chang etal. discloses a chemical composition and method for converting injectedfracturing fluid into a permeable proppant pack in-situ.

It would be advantageous to develop a fracturing fluid to improveconductivity of the proppant.

SUMMARY

In an embodiment the disclosure is directed to compositions and methodsfor fracturing treatment. The disclosure is specifically directed tofracture fluids and methods for fracturing a reservoir and in-situproppant generation using polymetric materials. The disclosed liquidsystem reacts to form proppant pillars in-situ under downholeconditions. Individual beads can also be generated. Hydrocarbon can flowto the wellbore for production through the channels between the proppantpillars. The proppant pillars can support the fractures and can providehigher hydraulic conductivity. This can be an alternative to a pulsedproppant fracturing method with formation of proppant pillars. In anembodiment, the beads can form downhole instead of forming at thesurface and being pumped downhole.

An embodiment of the disclosure is a hydraulic fracturing fluidcomprising a proppant for use in a downhole environment comprising aliquid solvent; at least one surfactant; a proppant-forming compound;and at least one curing agent; wherein the proppant forms pillars form atwo-dimensional structure capable of maintaining conductive fractures inthe downhole environment.

In an embodiment, the liquid solvent is selected from the groupconsisting of water, seawater, brine containing monovalent, divalent,and multivalent salts, an alcohol such as ethanol, propanol, andbutanol, and combinations thereof.

In an embodiment, the surfactant is selected from the group consistingof anionic surfactants, cationic surfactants, nonionic surfactants,amphoteric surfactants and combinations thereof.

In an embodiment, the proppant-forming compound is selected from thegroup consisting of aliphatic epoxides, anhydrides, glycidyl amineepoxide, cycloaliphatic epoxides, epoxy functional resins, polyurethaneresins, phenol-formaldehyde resin, bis-phenol A diglycidyl ether, polyglycidyl ethers, acrylic resin, glycidyl ethers, bis-phenol F diglycidylethernovalac resins, and combinations thereof.

In an embodiment, the curing agent is selected from the group consistingof isophorone diamine, boron tri-fluoride derivatives, imidazolines,mercaptans, hydrazides, polyamides, functional resins, mono ethanolamine, benzyl dimethylamine, lewis acids, tertiary amines,cycloaliphatic amines, amidoamines, aliphatic amines, aromatic amines,isophorone, imidazoles, sulfide, amides and their derivatives.

In an embodiment, the hydraulic fracturing fluid further comprises a pHcontrol agent. In an embodiment, the pH control agent is selected fromthe group consisting of mineral acids such as hydrochloric acid,sulfuric acid, nitric acid, and fluoroboric acid, sulfonic acids such asethanesulfonic acid and methanesulfonic acid, carboxylic acids such asacetic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide,and combinations thereof.

In an embodiment, the hydraulic fracturing fluid further comprises aviscosity modifier. In an embodiment, the viscosity modifiers isselected from the group consisting of nanoparticles such as calciumcarbonate nanoparticles and silicate nanoparticles, and water-solublepolymers such as polyacrylamide and polyvinyl alcohol.

In an embodiment, the hydraulic fracturing fluid further comprises astrength enhancing additive. In an embodiment, the strength enhancingadditive is selected from the group consisting of silicon particles,graphene particles, carbon black, and ceramic particles, and combinationthereof.

An embodiment of the disclosure wherein the hydraulic fracturing fluidcomprises 3 wt % Tween™ 20, 7 wt % Hostafrac SF14413, 30 wt % sea water,30 wt % Max CLR A resin, and 30 wt % Max CLR B curing agent. In anembodiment, the proppant forms individual solid beads.

An embodiment of the disclosure wherein the hydraulic fracturing fluidcomprises An embodiment of the disclosure wherein the hydraulicfracturing fluid comprises 31 wt % sea water, 31 wt % Max CLR A resin,31 wt % Max CLR B curing agent and 7 wt % Hostafrac SF 14504. In anembodiment, the proppant forms individual solid beads.

An embodiment of the disclosure wherein the hydraulic fracturing fluidcomprises 31 wt % sea water, 31 wt % Max CLR A resin, 31 wt % Max CLR Bcuring agent and 7 wt % Hyamine 1622. In an embodiment, the proppantforms a block.

An embodiment of the disclosure wherein the hydraulic fracturing fluidcomprises 23 wt % Poly(Bisphenol A-CO-Epichlorohydrin), GlycidylEnd-Capped, 50 wt % 10% Sodium chloride solution, 5 wt % Tomamine 12surfactant, 5 wt % 50% Sodium hydroxide, 15 wt % Mackazoline T, and 2 wt% Isophorone diamine. In an embodiment, the proppant forms agglomeratedpillars.

An embodiment of the disclosure wherein the hydraulic fracturing fluidcomprises 1.7 wt % Tween 20, 0.5 wt % Hostafrac SF14413, 37.8 wt %seawater, 30 wt % Max CLR A, and 30 wt % Max CLR B. In an embodiment,the proppant forms big pieces and individual beads.

An embodiment of the disclosure wherein the hydraulic fracturing fluidcomprises 3.5 wt % Tween 20, 1.5 wt % Hostafrac SF14413, 65 wt %seawater, 17 wt % Max CLR A, and 13 wt % Max CLR B. In an embodiment,the proppant forms pillars.

An embodiment of the disclosure is a method of hydraulic fracturingcomprising pumping the hydraulic fracturing fluid downhole.

An embodiment of the disclosure is a method of fracturing a reservoirwith a hydraulic fracturing fluid that generates fractures in thereservoir, the method comprising the steps of: mixing a liquid solvent,one or more surfactants, a proppant-forming compound, and one or morecuring agents to form a liquid composition; pumping the liquidcomposition into an injection well in the reservoir at an externalpressure to generate fractures in the reservoir; allowing the liquidcomposition to react to form in-situ proppants, wherein the in-situproppants are operable to keep the fractures open after the externalpressure is released.

In an embodiment, the liquid solvent is selected from the groupconsisting of water, seawater, brine containing monovalent, divalent,and multivalent salts, an alcohol such as ethanol, propanol, andbutanol, and combinations thereof.

In an embodiment, the surfactant is selected from the group consistingof anionic surfactants, cationic surfactants, nonionic surfactants,amphoteric surfactants and combinations thereof.

In an embodiment, the proppant-forming compound is selected from thegroup consisting of aliphatic epoxides, anhydrides, glycidyl amineepoxide, cycloaliphatic epoxides, epoxy functional resins, polyurethaneresins, phenol-formaldehyde resin, bis-phenol A diglycidyl ether, polyglycidyl ethers, acrylic resin, glycidyl ethers, bis-phenol F diglycidylethernovalac resins, and combinations thereof.

In some embodiments, the method further comprises the step of adding apH control agent to the liquid composition. In an embodiment, the pHcontrol agent is selected from the group consisting of mineral acidssuch as hydrochloric acid, sulfuric acid, nitric acid, and fluoroboricacid, sulfonic acids such as ethanesulfonic acid and methanesulfonicacid, carboxylic acids such as acetic acid, sodium hydroxide, potassiumhydroxide, calcium hydroxide, and combinations thereof.

In an embodiment, the method further comprises the step of adding aviscosity modifier to the liquid composition. In an embodiment, theviscosity modifiers is selected from the group consisting ofnanoparticles such as calcium carbonate nanoparticles and silicatenanoparticles, and water soluble polymers such as polyacrylamide andpolyvinyl alcohol.

In an embodiment, the method further comprises the step of adding astrength enhancing additive to the liquid composition. In an embodiment,the strength enhancing additive is selected from the group consisting ofsilicon particles, graphene particles, carbon black, and ceramicparticles, and combination thereof.

The foregoing has outlined rather broadly the features of the presentdisclosure in order that the detailed description that follows may bebetter understood. Additional features and advantages of the disclosurewill be described hereinafter, which form the subject of the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

In order that the manner in which the above-recited and otherenhancements and objects of the disclosure are obtained, a moreparticular description of the disclosure briefly described above will berendered by reference to specific embodiments thereof which areillustrated in the appended drawings. Understanding that these drawingsdepict only typical embodiments of the disclosure and are therefore notto be considered limiting of its scope, the disclosure will be describedwith additional specificity and detail through the use of theaccompanying drawings in which:

FIGS. 1(A), 1(B), and 1(C). FIGS. 1(A) and 1(B) depict simplifiedschematic illustrating proppant pillars to maintain the width of thefracture. FIG. 1(A) depicts a side view of the proppant pillars. FIG.1(B) depicts a top view of the propant pillars. The hydrocarbon flowsthrough the channels to the wellbore for production. FIG. 1(C) depicts aconventional proppant pack which depends on its porosity to providehydraulic conductivity;

FIG. 2 depicts liquid system 1 after mixing at RT;

FIG. 3 depicts the proppant product of liquid system 1 after heating at60° C. for 1 hour;

FIG. 4 depicts the proppant product of liquid system 2 after heating at60° C. for 1 hour;

FIG. 5(A)-5(H) depict reaction mixtures containing various surfactantsafter 1 hour at 60° C.; the reaction mixtures contain surfactants asfollows: 5(A) Hyamine 1622, 5(B) Tomanine 12, 5(C) Tomadol 902, 5(D)Mega Surf 101, 5(E) ASP 133, 5(F) 6191X, 5(G) Hostafrac SF 14413, 5(H)Hostafrac SF 14334.

FIG. 6 depicts products of agglomerated beads or islands;

FIG. 7 depicts products of some big pieces with some individual beads;and

FIG. 8 depicts structure of proppant pillars (white) and channelscreated in a slot to mimic the hydraulic fractures.

DETAILED DESCRIPTION

The particulars shown herein are by way of example and for purposes ofillustrative discussion of the preferred embodiments of the presentdisclosure only and are presented in the cause of providing what isbelieved to be the most useful and readily understood description of theprinciples and conceptual aspects of various embodiments of thedisclosure. In this regard, no attempt is made to show structuraldetails of the disclosure in more detail than is necessary for thefundamental understanding of the disclosure, the description taken withthe drawings making apparent to those skilled in the art how the severalforms of the disclosure may be embodied in practice.

The following definitions and explanations are meant and intended to becontrolling in any future construction unless clearly and unambiguouslymodified in the following examples or when application of the meaningrenders any construction meaningless or essentially meaningless. Incases where the construction of the term would render it meaningless oressentially meaningless, the definition should be taken from Webster'sDictionary 3^(rd) Edition.

The present disclosure describes a hydraulic fracturing fluid. The fluidwill lead to the formation of proppant in bead or pillar geometry underdownhole conditions. By selecting various surfactants, beads and/or bigpieces can be created. By pumping the liquid into a reservoir undersufficient external pressure, the liquid can fracture the formation andthen form in-situ proppant in the fracture without the need of pumpingconventional proppant with viscous fracturing fluid. Thus, it can reduceor eliminate the issue of proppant settling in the wellbore and thedamage associated with conventional fracturing fluids. Also, theproppant in pillar geometry has higher mechanical strength than proppantclusters made of the same materials. Furthermore, the proppant in pillarstructure forms a structure with channels of high conductivity forhydrocarbon to flow to the wellbore for production.

The size range of the proppant is very important for hydraulic fracturetreatment. Proppant size is generally between 8 and 140 mesh (105 μm to2.38 mm). Typically, larger particle sizes provide higher fractureconductivity. The traditional fracture treatment will start with smallerparticle size proppant and tailor with larger particle size proppant tomaximize the near wellbore conductivity. The in-situ formed proppantparticles can be significantly larger than conventional proppantparticles. Referring to FIG. 1(A) and FIG. 1(B), proppant particlesgenerated by the hydraulic fracturing fluid of the present disclosureform a pillar geometry structure. The proppant pillar geometrystructures comprises proppant pillars with channels between them forformation fluids to flow. In an embodiment, the proppant formed is largein size. In an embodiment, the width of the hydraulic fracture is mainlymaintained by separated proppant pillars, as opposed to proppantclusters. Larger particle size and the pillar geometry structure canhelp to improve fracture conductivity.

In an embodiment, the hydraulic fracturing fluid includes a liquidsolvent, one or more surfactants, a proppant-forming compound, and oneor more curing agents. In some embodiments, the liquid solvent can beaqueous solvents and non-aqueous solvents. Certain aqueous solventsinclude, but are not limited to, water, seawater, brine containingmonovalent, divalent, and multivalent salts. Certain non-aqueoussolvents include, but are not limited to, alcohol such as ethanol,propanol, and butanol, and combinations thereof.

Examples of proppant-forming compounds include, but are not limited to,aliphatic epoxides, anhydrides, glycidyl amine epoxide, cycloaliphaticepoxides, epoxy functional resins, polyurethane resins,phenol-formaldehyde resin, bis-phenol A diglycidyl ether, poly glycidylethers, acrylic resin, glycidyl ethers, bis-phenol F diglycidylethernovalac resins, and combinations thereof. In a preferredembodiment, the proppant-forming compound includes Max CLR™ A resin. MaxCLR™ is a trademark of Polymer Composites Corporation. Max CLR™ A is amodified bisphenol A epoxy resin, 90-100% by weight phenol,4-(1-methylethylidene) Bis, Polymer with (Chloromethane) Oxerane, 1-5%by weight epoxidize diluent reactive, 0-10% by weight epoxidizecresylglyciderether modified, and 0.1-0.5% by weight non-siliconeadditive.

Surfactants can be anionic surfactants, cationic surfactants, nonionicsurfactants, amphoteric surfactants and combinations thereof. In anembodiment, the surfactant includes Hostafrac SF14504 and HostafracSF14413. Hostafrac is a trademark of Clariant International Ltd.Hostafrac SF14413 is a product of Clariant Corporation and is 10-20% byweight proprietary ingredient 6615, 10-20% by weight ethoxylatedisotridecanol, 1-10% proprietary ingredient 6715, 1-5% solvent naphtha,0.1-1% by weight naphthalene.

Certain examples of curing agent include, but are not limited toisophorone diamine, boron tri-fluoride derivatives, imidazolines,mercaptans, hydrazides, polyamides, functional resins, mono ethanolamine, benzyl dimethylamine, Lewis acids, tertiary amines,cycloaliphatic amines, amidoamines, aliphatic amines, aromatic amines,isophorone, imidazoles, sulfide, amides and their derivatives. In anembodiment, the curing agent includes Max CLR™ B. Max CLR is a trademarkof Polymer Composites Corporation. Max CLR B is an amine modified curingagent. It contains about between 5-15% by weight benzyl alcohol, 15-35%by weight isophoromediamine adduct, and 50-60% by weight aliphatic amineadduct.

In some embodiments, pH control agents and viscosity modifiers may beadded into the liquid solvent. Certain examples of pH control agentsinclude but are not limited to mineral acids such as hydrochloric acid,sulfuric acid, nitric acid, and fluoroboric acid, sulfonic acids such asethanesulfonic acid and methanesulfonic acid, carboxylic acids such asacetic acid, sodium hydroxide, potassium hydroxide, calcium hydroxide,and combinations thereof. Examples of viscosity modifiers include butare not limited to nanoparticles such as calcium carbonate nanoparticlesand silicate nanoparticles, and water-soluble polymers such aspolyacrylamide and polyvinyl alcohol.

In some embodiments, the hydraulic fracturing fluid further includesstrength enhancing additives to improve the strength of the proppant. Inan embodiment, the strength enhancing additives can be selected fromsilicon particles, graphene particles, carbon black, ceramic particles,and combinations thereof.

EXAMPLES

Several fluid candidates forming in-situ proppants were evaluated asfollows:

Example 1

Table 1 lists the components of liquid system 1. Liquid system 1includes 3 wt % Tween™ 20 (surfactant), 7 wt % Hostafrac SF14413(another surfactant), 30 wt % sea water, 30 wt % Max CLR A resin, and 30wt % Max CLR B curing agent. Tween™ is a registered trademark of CrodaInternational plc, and contains alkoxylate. Hostafrac. SF14413 is aproduct of Clariant Corporation. It includes 10-20% by weightproprietary ingredient 6615, 10-20% by weight ethoxylated isotridecanol,1-10% proprietary ingredient 6715, 1-5% solvent naphtha, and 0.1-1% byweight naphthalene. Max CLR™ is a trademark of Polymer CompositesCorporation. Max CLR™ A is a modified bisphenol A epoxy resin, 90-100%by weight phenol, 4-(1-methylethylidene) Bis, Polymer with(Chloromethane) Oxerane, 1-5% by weight epoxidize diluent reactive,0-10% by weight epoxidize cresylglyciderether modified, and 0.1-0.5% byweight non-silicone additive. Max CLR™ B is an amine modified curingagent. It contains about between 5-15% by weight benzyl alcohol, 15-35%by weight isophoromediamine adduct, and 50-60% by weight aliphatic amineadduct.

TABLE 1 Liquid components Wt. % Tween ™ 20 3 Hostafrac SF14413 7Seawater 30 Max CLR ™ A 30 Max CLR ™ B 30

All components are in liquid form and mixed at room temperature (RT).Room temperature is the range of air temperatures that most peopleprefer for indoor settings. The range is between 15° C. and 25° C.Liquid system 1 was mixed for 15 minutes (FIG. 2) and then the mixturewas heated undisturbed at 60 degrees Celsius in a water bath for 1 hour.Individual solid beads were generated (FIG. 3). FIG. 3 shows the solidbeads after being air dried at RT. The effective liquid to solidconversion rate (ELSCR) can be over 95%. The ELSCR is defined as theweight of the solid particles generated divided by the weight of MaxCLR™ A with Max CLR™ B. The beads were tested for crush resistance andacid solubility according to ISO 13503-2. The fine generated was lessthan 3% with a closure stress up to 10,000 psi. The acid dissolution wasless than 3%.

Two surfactants Tween™ 20 and Hostafrac SF14413 were used together tocreate the individual solid beads. The advantage of using twosurfactants rather than one is that the Hydrophile-Lipophile Balance(HLB) value can be well adjusted by changing the ratio of thesurfactants to control the coalescence rate of emulsion to generatedesired products.

Example 2

The components of liquid system 2 are listed in Table 2. Liquid system 2includes 31 wt % sea water, 31 wt % Max CLR A resin, 31 wt % Max CLR Bcuring agent and 7 wt % Hostafrac SF 14504. Hostafrac is a trademark ofClariant International Ltd. Hostafrac SF14504 is a surfactant product ofClariant Corporation. It includes less than 5% ethoxylated alcohol, lessthan 10% polyoxylene monobutyl ether, and less than 5% polylene glycol.All components are in liquid form and mixed in a plastic cup at roomtemperature. The mixture was heated undisturbed at 60 degrees Celsius ina water bath for 1 hour to generate individual solid beads (FIG. 4).

TABLE 2 Liquid chemicals Wt. % Hostafrac SF 14504 7% surfactant Seawater 31% Max CLR A resin 31% Max CLR B curing agent 31%

Example 3

The components of liquid system 3 are listed in Table 3. Liquid system 3includes 31 wt % sea water, 31 wt % Max CLR A resin, 31 wt % Max CLR Bcuring agent and 7 wt % Hyamine 1622. Hyamine is a registered trademarkof Lonza Group, Ltd. Hyamine 1622 is a surfactant comprising cationicdetergent benzethonium chloride. All components are in liquid form andmixed in a plastic cup at room temperature.

TABLE 3 Liquid chemicals Wt. % Hyamine 1622 7% Sea water 31% Max CLR Aresin 31% Max CLR B curing agent 31%

The mixture was heated undisturbed at 60 degrees Celsius in a water bathfor 1 hour. After that, a whole block was formed instead of individualsolid beads (FIG. 5(A)). When Hyamine 1622 was replaced with othersurfactants listed in Table 4 and the mixtures were heated undisturbedat 60 degrees Celsius in a water bath for 1 hour, these products wereformed into whole blocks (FIG. 5(B)-5(H)). These in-situ formed blockscan serve the purpose of supporting the fracture like proppant pillars(FIGS. 1(A) and 1(B)). FIG. 5(B) shows reaction product containingTOMANINE 12, FIG. 5(C) shows reaction product containing Tomadol 902,FIG. 5(D) shows reaction product containing Mega Surf 101, FIG. 5(E)shows reaction product containing ASP 133, FIG. 5(F) shows reactionproduct containing 6191X, FIG. 5(G) shows reaction product containingHostafrac SF 14413, and FIG. 5(H) shows reaction product containingHostafrac SF 14334. MegaSurf 101 is a surfactant made by ShrieveChemical Company; TOMADOL 902 and TOMANINE 12 are surfactants made byAir Products; ASP133 and CorsiTech 6191X are surfactants made by Nalco;Bio-Terge AS-40 is a surfactant made by Stepan; Hostafrac SF 14334 andHostafrac SF 14413 are surfactants made by Clariant.

TABLE 4 Surfactant Vendor Surfactant Name Air Products TOMANINE 12 AirProducts TOMADOL 902 Shrieve MegaSurf 101 Nalco ASP133 Nalco CorsiTech6191X Clariant Hostafrac SF 14413 Clariant Hostafrac SF 14334

Example 4

Table 5 lists the components of liquid system 4. Liquid system 4includes 23 wt % Poly(Bisphenol A-CO-Epichlorohydrin), GlycidylEnd-Capped, 50 wt % 10% Sodium chloride solution, 5 wt % Tomamine 12surfactant, 5 wt % 50% Sodium hydroxide, 15 wt % Mackazoline T, and 2 wt% Isophorone diamine.

TABLE 5 Liquid chemicals Wt. % Poly(Bisphenol A-CO-Epichlorohydrin), 23%Glycidyl End-Capped 10% Sodium chloride 50% solution Tomamine 12surfactant 5% 50% Sodium hydroxide 5% Mackazoline T 15% Isophoronediamine 2%

Poly (Bisphenol A-CO-Epichlorohydrin), Glycidyl End-Capped (AverageMn-355) is a resin with molecular formula (C₁₈H₂₂O₃)n. C₂₂H₂₆O₄;Tomamine 12 surfactant contains 65% water and 35% “alkyl iminodipropionic acid, monosodium salt”; Mackazoline T contains 95-99% “Talloil hydroxyethyl imidazoline” and 1-5% aminoethylethanolamine.

All components are in liquid form and mixed in a plastic cup at roomtemperature. The mixture was heated undisturbed at 60 degrees Celsius ina water bath for 1 hour. FIG. 6 shows the reaction product of liquidsystem 4. The product will form agglomerated beads or islands. Thesein-situ formed bead islands can serve the purpose of supporting thefracture like proppant pillars.

Example 5

Table 6 lists the components of liquid system 5. Liquid system 5includes 1.7 wt % Tween 20, 0.5 wt % Hostafrac SF14413, 37.8 wt %seawater, 30 wt % Max CLR A, and 30 wt % Max CLR B.

TABLE 6 Liquid components Wt. % Tween ™ 20 1.7 Hostaffac SF14413 0.5Seawater 37.8 Max CLR ™ A 30 Max CLR ™ B 30

Liquid system 5 was mixed for 15 minutes in a plastic cup and allowed tostand undisturbed in water bath at 60° C. for 1 hour to react. It formeda proppant in big pieces with some individual beads formed as shown inFIG. 7. The in-situ formed big pieces can serve the purpose ofsupporting the fracture like proppant pillars.

Example 6

Table 7 lists the components of liquid system 6. Liquid system 6includes 3.5 wt % Tween 20, 1.5 wt % Hostafrac SF14413, 65 wt %seawater, 17 wt % Max CLR A, and 13 wt % Max CLR B.

TABLE 7 Liquid components Wt. % Tween ™ 20 3.5 Hostafrac SF14413 1.5Seawater 65 Max CLR ™ A 17 Max CLR ™ B 13

Liquid system 6 was mixed for 5 minutes in a plastic cup, pumped into aslot made of one clear tempered glass and one satin-etched temperedglass parallel to each other with a gap width of 1/16 inch to mimic ahydraulic fracture, and then allowed to stand undisturbed in an oven at60° C. for 3 hour to react to form proppant pillars and channelsstructures as shown in FIG. 8. The proppant pillars are to maintain thewidth of the hydraulic fractures created, and the channels are forhydrocarbon to flow through the wellbore for production as indicated inFIG. 1(B).

Wherein Tween™ is a registered trademark of Croda International plc,containing Alkoxylate. Hostafrac SF14413 is a product of ClariantCorporation. 10-20% by weight proprietary ingredient 6615, 10-20% byweight ethoxylated isotridecanol, 1-10% proprietary ingredient 6715,1-5% solvent naphtha, and 0.1-1% by weight naphthalene.

Max CLR™ is a trademark of Polymer Composites Corporation. Max CLR™ A isa modified bisphenol A epoxy resin, 90-100% by weight phenol,4-(1-methylethylidene) Bis, Polymer with (Chloromethane) Oxerane, 1-5%by weight epoxidize diluent reactive, 0-10% by weight epoxidizecresylglyciderether modified, and 0.1-0.5% by weight non-siliconeadditive. Max CLR™ B is an amine modified curing agent. It containsabout between 5-15% by weight benzyl alcohol, 15-35% by weightisophoromediamine adduct, and 50-60% by weight aliphatic amine adduct.

All of the compositions and methods disclosed and claimed herein can bemade and executed without undue experimentation in light of the presentdisclosure. While the compositions and methods of this disclosure havebeen described in terms of preferred embodiments, it will be apparent tothose of skill in the art that variations may be applied to thecompositions and methods and in the steps or in the sequence of steps ofthe methods described herein without departing from the concept, spiritand scope of the disclosure. More specifically, it will be apparent thatcertain agents which are both chemically related may be substituted forthe agents described herein while the same or similar results would beachieved. All such similar substitutes and modifications apparent tothose skilled in the art are deemed to be within the spirit, scope andconcept of the disclosure as defined by the appended claims.

1. A method of hydraulic fracturing comprising formulating a hydraulicfracturing fluid comprising a liquid solvent, at least one surfactant, aliquid phase proppant-forming compound, and at least one curing agent;injecting the hydraulic fracturing fluid into a wellbore; wherein theproppant is generated from a liquid system in-situ under down holeconditions; and wherein the liquid phase proppant-forming compound formspillars in a two-dimensional structure capable of maintaining conductivefractures in the downhole environment.
 2. The method of claim 1, whereinthe liquid solvent is selected from the group consisting of water,seawater, brine containing monovalent, divalent, and multivalent salts,an alcohol such as ethanol, propanol, and butanol, and combinationsthereof.
 3. The method of claim 1, wherein the surfactant is selectedfrom the group consisting of anionic surfactants, cationic surfactants,nonionic surfactants, amphoteric surfactants and combinations thereof.4. The method of claim 1, wherein the proppant-forming compound isselected from the group consisting of aliphatic epoxides, anhydrides,glycidyl amine epoxide, cycloaliphatic epoxides, epoxy functionalresins, polyurethane resins, phenol-formaldehyde resin, bis-phenol Adiglycidyl ether, poly glycidyl ethers, acrylic resin, glycidyl ethers,bis-phenol F diglycidyl ethernovalac resins, and combinations thereof.5. The method of claim 1, wherein the curing agent is selected from thegroup consisting of isophorone diamine, boron tri-fluoride derivatives,imidazolines, mercaptans, hydrazides, polyamides, functional resins,mono ethanol amine, benzyl dimethylamine, lewis acids, tertiary amines,cycloaliphatic amines, amidoamines, aliphatic amines, aromatic amines,isophorone, imidazoles, sulfide, amides and their derivatives.
 6. Themethod of claim 1, further comprising a pH control agent.
 7. The methodof claim 6, wherein the pH control agent is selected from the groupconsisting of mineral acids, fluoroboric acid, sulfonic acids,carboxylic acids and combinations thereof.
 8. The method of claim 1,further comprising a viscosity modifier.
 9. The method of claim 8,wherein the viscosity modifier is selected from the group consisting ofnanoparticles and water-soluble polymers.
 10. The method of claim 1,further comprising a strength enhancing additive.
 11. The method ofclaim 10, wherein the strength enhancing additive is selected from thegroup consisting of silicon particles, graphene particles, carbon black,ceramic particles, and combination thereof.
 12. The method of claim 1,comprising: 3 wt % Polyoxyethylene (20) sorbitan monolaurate, 7 wt %Hostafrac SF14413, 30 wt % sea water, 30 wt % resin comprising: 90-100%Phenol, 4-(1-methylethylidene) Bis, polymer with (chloromethane)Oxecrane, 1-20% epoxide Diluent, 0-10% Modified Epoxy Novalac, 0.1-0.5%Non-Silicone Additive, and 30 wt % curing agent comprising: 5-15% BenzylAlcohol, 15-35% isophoronediamine adduct, 50-60% Aliphatic amine adduct.13. The method of claim 1 wherein in the hydraulic fracturing fluidfurther comprises: 31 wt % sea water, 31 wt % resin comprising: 90-100%Phenol, 4-(1-methylethylidene) Bis, polymer with (chloromethane)Oxecrane, 1-20% epoxide Diluent, 0-10% Modified Epoxy Novalac, 0.1-0.5%Non-Silicone Additive, 31 wt % curing agent comprising: 5-15% BenzylAlcohol, 15-35% isophoronediamine adduct, 50-60% Aliphatic amine adduct.and 7 wt % Hostafrac SF
 14504. 14. The method of claim 11 wherein in thehydraulic fracturing fluid further comprises: 31 wt % sea water, 31 wt %resin comprising: 90-100% Phenol, 4-(1-methylethylidene) Bis, polymerwith (chloromethane) Oxecrane, 1-20% epoxide Diluent, 0-10% ModifiedEpoxy Novalac, 0.1-0.5% Non-Silicone Additive, 31 wt % curing agentcomprising: 5-15% Benzyl Alcohol, 15-35% isophoronediamine adduct,50-60% Aliphatic amine adduct 7 wt % cationic detergent comprising 99%benzethonium chloride and 1% water.
 15. The method of claim 1,comprising 23 wt % Poly(Bisphenol A-CO-Epichlorohydrin), GlycidylEnd-Capped, 50 wt % 10% Sodium chloride solution, 5 wt % surfactantcomprising 35% alkyl imino dipropionic acid, monosodium salt in 65%water, 5 wt % 50% Sodium hydroxide, 15 wt % fatty amine comprising95-99% tall oil hydroxyethyl imidazoline and 1-5%aminoethylethanolamine, and 2 wt % Isophorone diamine.
 16. The method ofclaim 1 wherein the fracturing fluid further comprises: comprising 1.7wt % Polyoxyethylene (20) sorbitan monolaurate, 0.5 wt % HostafracSF14413, 37.8 wt % seawater, 30 wt % resin comprising: 90-100% Phenol,4-(1-methylethylidene) Bis, polymer with (chloromethane) Oxecrane, 1-20%epoxide Diluent, 0-10% Modified Epoxy Novalac, 0.1-0.5% Non-SiliconeAdditive, and 30 wt % curing agent comprising: 5-15% Benzyl Alcohol,15-35% isophoronediamine adduct, 50-60% Aliphatic amine adduct
 17. Themethod of claim 1, comprising 3.5 wt % Polyoxyethylene (20) sorbitanmonolaurate, 1.5 wt % Hostafrac SF14413, 65 wt % seawater, 17 wt % resincomprising: 90-100% Phenol, 4-(1-methylethylidene) Bis, polymer with(chloromethane) Oxecrane, 1-20% epoxide Diluent, 0-10% Modified EpoxyNovalac, 0.1-0.5% Non-Silicone Additive, and 13 wt % curing agentcomprising: 5-15% Benzyl Alcohol, 15-35% isophoronediamine adduct,50-60% Aliphatic amine adduct.
 18. The method of claim 1, wherein theproppant forms individual solid beads.
 19. (canceled)
 20. (canceled)